US7612245B2 - Method for selective hydrogenation of polyunsaturated compounds into monounsaturated compounds using a homogeneous catalyst - Google Patents
Method for selective hydrogenation of polyunsaturated compounds into monounsaturated compounds using a homogeneous catalyst Download PDFInfo
- Publication number
- US7612245B2 US7612245B2 US10/519,355 US51935505A US7612245B2 US 7612245 B2 US7612245 B2 US 7612245B2 US 51935505 A US51935505 A US 51935505A US 7612245 B2 US7612245 B2 US 7612245B2
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- US
- United States
- Prior art keywords
- process according
- ligand
- butadiene
- transition metal
- butene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related, expires
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 32
- 239000002815 homogeneous catalyst Substances 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 239000003446 ligand Substances 0.000 claims abstract description 35
- 230000008569 process Effects 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 20
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000002608 ionic liquid Substances 0.000 claims abstract description 8
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 8
- 150000003624 transition metals Chemical class 0.000 claims abstract description 8
- 150000001450 anions Chemical class 0.000 claims abstract description 5
- 125000002524 organometallic group Chemical group 0.000 claims abstract description 5
- 230000000737 periodic effect Effects 0.000 claims abstract description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 95
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 39
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 38
- -1 transition metal salt Chemical class 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 229910052742 iron Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 7
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- 229910052785 arsenic Inorganic materials 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000012429 reaction media Substances 0.000 claims description 6
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- 239000010949 copper Substances 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
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- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
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- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 125000005534 decanoate group Chemical class 0.000 claims description 2
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- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- INDFXCHYORWHLQ-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-butyl-3-methylimidazol-3-ium Chemical compound CCCCN1C=C[N+](C)=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F INDFXCHYORWHLQ-UHFFFAOYSA-N 0.000 description 1
- XHIHMDHAPXMAQK-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F XHIHMDHAPXMAQK-UHFFFAOYSA-N 0.000 description 1
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 1
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 description 1
- QFMZQPDHXULLKC-UHFFFAOYSA-N c1ccc(P(CCP(c2ccccc2)c2ccccc2)c2ccccc2)cc1 Chemical compound c1ccc(P(CCP(c2ccccc2)c2ccccc2)c2ccccc2)cc1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- WUOIAOOSKMHJOV-UHFFFAOYSA-N ethyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CC)C1=CC=CC=C1 WUOIAOOSKMHJOV-UHFFFAOYSA-N 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- ZJXKJXNVHCQBTO-UHFFFAOYSA-N n,n'-bis(2,6-dimethylphenyl)ethane-1,2-diimine Chemical compound CC1=CC=CC(C)=C1N=CC=NC1=C(C)C=CC=C1C ZJXKJXNVHCQBTO-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004817 pentamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- NNLBHYFYTVCQBR-UHFFFAOYSA-N pyridine;sulfurofluoridic acid Chemical compound [O-]S(F)(=O)=O.C1=CC=[NH+]C=C1 NNLBHYFYTVCQBR-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- YCBRTSYWJMECAH-UHFFFAOYSA-N tributyl(tetradecyl)phosphanium Chemical compound CCCCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC YCBRTSYWJMECAH-UHFFFAOYSA-N 0.000 description 1
- ZNEOHLHCKGUAEB-UHFFFAOYSA-N trimethylphenylammonium Chemical compound C[N+](C)(C)C1=CC=CC=C1 ZNEOHLHCKGUAEB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
- C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
- C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
- C10G45/36—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
- C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
- C10G45/40—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing platinum group metals or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
Definitions
- the present invention relates to hydrogenating diolefinic compounds to monoolefinic compounds.
- Hydrocarbon conversion processes such as steam cracking, visbreaking, catalytic cracking and cokefaction are carried out at high temperatures to allow a large quantity of unsaturated compounds the formation of which is favoured at high temperatures to be formed: acetylenic compounds (acetylene, propyne, vinyl- and ethyl-acetylene), diolefinic compounds such as 1,2-propadiene, 1,2-butadiene and 1,3-butadiene, olefinic compounds such as ethylene, propylene, 1-n-butene, 2-n-butenes, isobutene, pentenes and other compounds the boiling point of which is in the “gasoline” cut range and which may be olefinic or diolefinic.
- acetylenic compounds acetylene, propyne, vinyl- and ethyl-acetylene
- diolefinic compounds such as 1,2-propadiene, 1,2-butadiene and 1,3-butadiene
- the most highly unsaturated compounds are highly unstable and very readily produce high molecular weight products (oligomers, gums) by polymerization reactions. Such highly unsaturated compounds must therefore be eliminated to allow different cuts derived from said processes to be used for chemistry or for olefin polymerization processes.
- the steam cracking C 4 cut contains a high proportion of 1,3-butadiene which must be eliminated before it can be used in butene polymerization units.
- methylacetylene (MA) and propadiene (PD) compounds present in the C 3 steam cracking cut in an amount of 3% to 4% by weight must be eliminated before the propylene can be used to synthesize polypropylene.
- 1,3-butadiene is separated from the olefinic cut, for example by extractive distillation in the presence of dimethylformamide or N-methyl-pyrrolidone.
- the olefinic cut obtained contains isobutane, isobutene, 1-butene, 2-butenes, n-butane and 1,3-butadiene, this latter being in an amount of between 0.1% and 2% by weight.
- the cut can be treated directly over a catalyst in the presence of hydrogen to transform the 1,3-butadiene into n-butenes.
- 2-butene is desired, processes which can produce a great deal of 2-butene and separate different compounds must be used, such as selective hydrogenation of 1,3-butadiene to butanes with a high degree of isomerization of 1-butene to 2-butene.
- 2-butene is used as a feedstock for petrochemicals. That type of use necessitates almost complete hydrogenation of the 1,3-butadiene as its presence can only be tolerated in amounts of less than 10 ppm by weight.
- a further application that can be envisaged is the reduction in the 1,3-butadiene content in a 1-butene rich cut without transforming the latter into butane or isomerizing it to 2-butene, cis and/or trans. That reaction can be integrated into a 1-butene production process carried out in a finishing reactor which can reduce the 1,3-butadiene content to less than 10 ppm.
- this hydrogenation rate is relatively low, and the kinetics are generally negative with respect to the acetylenic compound.
- consecutive hydrogenation of 1-butene is carried out at a much higher rate than hydrogenation of the acetylenic compound.
- diene hydrogenation rate is generally close to that of the olefin when the molecules are not mixed or hydrogenated consecutively.
- That phenomenon poses a certain number of problems as regards industrial units.
- very high 1,3-butadiene conversions are required. This has the effect of greatly reducing the concentration of 1,3-butadiene in the reactor and in particular at the outlet, to values which are lower than those corresponding to covering the catalyst surface completely.
- olefinic molecules have access to the active surface and as their hydrogenation rate is of the same order as that of 1,3-butadiene, they are consumed.
- a large quantity of 1,3-butadiene is transformed into butane.
- the aim of the invention is to provide a liquid catalytic composition which allows selective hydrogenation of polyunsaturated compounds to monounsaturated compounds.
- Said catalytic composition allows hydrogenation of diolefinic compounds to mono-olefinic compounds at rates which are at least 3 times and generally about 5 times higher than the hydrogenation rate of ⁇ -olefinic compounds to saturated compounds.
- This soluble catalyst can be generally defined as comprising at least one salt of a transition metal from groups IB, IIB, VB, VIB, VIIB and VIII, at least one ligand and at least one organometallic reducing agent.
- the catalytic composition used in the process of the invention is characterized:
- nitrogen-containing ligands which can be cited are amines and polyamines, imidazole, substituted imidazoles, pyrrole and substituted pyrroles, pyrazoles, amide derivatives, imines or diimines (produced, for example, by reacting glyoxal with a derivative of aniline substituted on the aromatic ring), and finally pyridine derivatives.
- R′ H or CH 3
- n 1, 2 or 3 or 4
- R alkyl, aryl or aryl partially substituted with 1, 2, 3 or 4 methyl, ethyl, isopropyl or methoxy groups.
- the ligands can also carry a function such as ammonium, phosphonium, a carboxylic acid, an amine, an alcohol or a sulphonate.
- an organic compound can be used to act as a solvent; the following can act as solvents: aliphatic or aromatic hydrocarbons, ethers, esters, halogenated hydrocarbons and, at low concentrations, sulphoxides and amides; the reaction can also be carried out in the absence of an additional solvent; it is then the polyunsaturated or monounsaturated compound which acts as a solvent.
- At least one salt of another transition metal selected for example if the principal metal is a metal from group VIII) from metals from groups IB, VB, VIB, VIIB and VIII, more particularly (for example if the principal metal is iron) from Co, Ni, Cu, Rh, Pd, Mn, Mo, W and V, preferably from Ni, Cu, Rh and Pd, can be added to the hydrogenation catalyst.
- the additional metal is introduced in a minor proportion with respect to the principal metal.
- the invention also concerns a catalytic composition
- a catalytic composition comprising at least one compound of a transition metal from groups IB, IIB, VB, VIB, VIIB and VIII, at least one ligand, at least one reducing agent and at least one ionic liquid with formula Q + A ⁇ , as defined below.
- Said solvents which are constituted solely by ions, have physico-chemical properties, in particular their solubility with organic compounds, which can be modified as a function of the choice of anion and cation.
- Their application in catalysis has been reviewed several times; the most recent is that by R Sheldon, Chem. Commun 2001, 2399. It is then possible to select the ionic liquid so that the products from the reaction are less miscible in the ionic liquid in which the catalyst is dissolved. The reaction thus carried out in a two-phase medium. The products can readily be separated from the catalyst and solvent by simple decanting. The catalyst and the solvent can be recycled.
- complexes of transition metals from groups IB, IIB, VB, VIB, VIIB and VIII, preferably iron, associated with a ligand, in an ionic liquid with general formula Q + A ⁇ are capable of hydrogenating unsaturated derivatives, in particular diolefins with improved selectivities and activities.
- the ligand is preferably a nitrogen-containing ligand selected, for example, from those described above.
- the non-aqueous ionic liquid is selected from the group formed by liquid salts with general formula Q + A ⁇ in which Q + represents a quaternary ammonium and/or quaternary phosphonium ion and A ⁇ represents any anion which is capable of forming a liquid salt at low temperatures, i.e. below 90° C. and advantageously at most 85° C., preferably below 50° C.
- the quaternary ammonium and/or phosphonium ions Q + preferably have general formulae NR 1 R 2 R 3 R 4+ and PR 1 R 2 R 3 R 4+ or general formulae R 1 R 2 N ⁇ CR 3 R 4+ and R 1 R 2 P ⁇ CR 3 R 4+ in which R 1 , R 2 , R 3 and R 4 , which may be identical or different, represent hydrogen (with the exception of the cation NH 4 + for NR 1 R 2 R 3 R 4+ ); preferably, a single substituent represents hydrogen or hydrocarbyl residues containing 1 to 30 carbon atoms, for example alkyl groups, saturated or non saturated groups cycloalkyl or aromatic groups, aryl or aralkyl groups, which may be substituted, containing 1 to 30 carbon atoms.
- ammonium and/or phosphonium ion can also be derived from nitrogen-containing and/or phosphorus-containing heterocycles comprising 1, 2 or 3 nitrogen and/or phosphorus atoms, with general formulae:
- the cycles are constituted by 4 to 10 atoms, preferably 5 to 6 atoms, R 1 and R 2 being as defined above.
- the quaternary ammonium or phosphonium can also be a cation with formula: R 1 R 2+ N ⁇ CR 3 —R 5 —R 3 C ⁇ N + R 1 R 2 or R 1 R 2+ P ⁇ CR 3 —R 5 —R 3 C ⁇ P + R 1 R 2 in which R 1 , R 2 and R 3 , which may be identical or different, are defined as above and R 5 represents an alkylene or phenylene residue.
- R 1 , R 2 , R 3 and R 4 which can be mentioned are methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, tertiary butyl, amyl, methylene, ethylidene, phenyl or benzyl radicals;
- R 5 may be a methylene, ethylene, propylene or phenylene group.
- the ammonium and/or phosphonium cation Q + is preferably selected from the group formed by N-butylpyridinium, N-ethylpyridinium, pyridinium, 3-ethyl-1-methylimidazolium, 3-butyl-1-methylimidazolium, 3-hexyl-1-methylimidazolium, 3-butyl-1,2-dimethylimidazolium, diethylpyrazolium, N-butyl-N-methylpyrrolidinium, trimethylphenylammonium, tetrabutylphosphonium and tributyl-tetradecylphosphonium.
- salts which can be used in the invention that can be cited are N-butylpyridinium hexafluorophosphate, N-ethylpyridinium tetrafluoroborate, pyridinium fluorosulphonate, 3-butyl-1-methylimidazolium tetrafluoroborate, 3-butyl-1-methylimidazolium hexafluoroantimonate, 3-butyl-1-methylimidazolium hexafluorophosphate, 3-butyl -1-methylimidazolium trifluoroacetate, 3-butyl-1-methylimidazolium trifluoromethylsulphonate, 3-butyl-1-methylimidazolium bis(trifluoromethylsulphonyl)amide, trimethylphenylammonium hexafluorophosphate and tetrabutylphosphonium tetrafluoroborate. These salts can be used alone or as a mixture.
- the mole ratio between the ligand and the transition metal salt is in the range 0.5/1 to 10/1, preferably in the range 0.5/1 to 3/1.
- the ligand is monocoordinating, it can usefully be used in a ligand/transition metal salt mole ratio of 2/1 to 3/1. If the ligand is bicoordinating, it is preferably used with a ligand/transition metal salt mole ratio of 1/1 to 1.5/1.
- the mole ratio between the reducing agent and the transition metal salt is generally 1/1 to 5/1, preferably 1.2/1 to 5/1.
- the catalyst can be prepared in two ways.
- the first consists of separately injecting the products into a stainless steel Grignard reactor containing the substrate to be hydrogenated.
- the second consists of preparing the mixture ex situ. This procedure has the advantage of allowing the possibility of monitoring the reduction state of the iron visually.
- TEA When TEA is injected into the flask containing the iron-diimine complex, it can be seen that the initially red solution becomes dark brown.
- a release of gas constituted by an ethane/ethylene mixture results from the reducing action of TEA.
- only a single injection per syringe is required into the catalysis reactor. The performances obtained in both operating modes are almost identical.
- the ligand in the presence of a diolefin, before adding the reducing agent. It is also possible to isolate a FeHXL2 (where L is an imine) or FeHXL′ (where L′ is a diimine) reduced iron complex in which X is a halogen, an acetylacetonate or a carboxylate and to add an alkylaluminium or any other reducing agent in the presence of a diolefin.
- L is an imine
- FeHXL′ where L′ is a diimine
- the catalytic composition is added to the system in catalytic quantities.
- This quantity expressed in ppm (parts per million) of metallic compounds in the reaction medium, is in the range 10 to 10000 ppm, preferably in the range 40 to 300 ppm.
- the reaction temperature is in the range 0° C. to 70° C., preferably in the range 10° C. to 30° C.
- the partial pressure of hydrogen is in the range 0 to 20 MPa, preferably in the range 0.01 to 5 MPa and more preferably in the range 0.5 to 1.5 MPa.
- the catalyst defined in the invention was obtained after mixing the three compounds in the following order: metal salt-ligand-reducing agent, in a mole ratio of 1/1/3 respectively.
- n-heptane a solution of iron salt in n-heptane from iron octoate, which is a viscous brown liquid constituted by iron III 2-ethylhexanoate in the presence of a slight excess of 2-ethylhexanoic acid in solution in dearomatized white spirit. That product titrated at 10% by weight of iron.
- a solution in n-heptane was prepared with a concentration of 0.7 g of iron/100 ml, i.e. 12.5 mMol/100 ml.
- diimine solution (ligand). 2,3-bis(2,6-dimethylphenylimino)butane, with the developed formula (1) shown in the paragraph describing the ligands was used.
- This diimine was dissolved in n-heptane at a concentration of 1.48 g/100 ml, i.e equivalent to 5 mMol/100 ml.
- Triethylaluminium [Al(Et) 3 ] or TEA
- TEA Triethylaluminium
- a dilute solution of triethylaluminium in heptane titrating 1.32 mMol/ml was used. It should be noted that the heptane used as the solvent to dissolve the reagents had to be dried in advance and stored over a molecular sieve to keep it anhydrous.
- the first test consisted of introducing in succession, using a syringe, into the Grignard reactor with gentle stirring containing a mixture constituted by 120 ml of n-heptane and 8.4 g of 1,3-butadiene maintained at a temperature of 17° C., 2.7 ml of the iron salt solution, then 6.7 ml of the diimine solution and finally 0.8 ml of the TEA solution.
- This catalytic composition corresponds to an iron composition of the order of 200 ppm with respect to the reaction medium.
- the Grignard reactor was then placed under 1 Mpa of hydrogen and stirring was increased to increase the solubility of hydrogen in the liquid phase.
- the hydrogen pressure was kept constant in the Grignard reactor and the hydrogen consumption was measured by the reduction in hydrogen pressure contained in an intermediate trap of known volume.
- This mode of operation allowed an estimation with a certain degree of accuracy to be made of the theoretical quantity of hydrogen necessary to convert all of the 1,3-butadiene employed and thus of being able to stop the reaction and/or take intermediate samples for analysis.
- hydrogenation of 8.4 g of 1,3-butadiene corresponded to a rapid reduction in pressure in the trap of 3 MPa of hydrogen. If hydrogenation was continued, the reaction rate corresponding to the conversion of butenes into butane was accompanied by a substantial reduction in hydrogen consumption.
- Example 1 The operating procedure of Example 1 was used, except that the catalyst was prepared outside the reactor and injected after ex situ reduction. Identical results were obtained as regards selectivity. The reaction time to reach 80% 1,3-butadiene conversion was increased by 20 seconds.
- Example 1 The operating procedure of Example 1 was used, except that half as much catalyst was introduced, i.e the equivalent of 100 ppm of iron instead of 200 ppm. At this catalyst concentration, 80% conversion was obtained in 120 seconds.
- Example 1 The operating procedure of Example 1 was used, except that an equivalent of 80 ppm of iron was introduced instead of the 200 ppm and 100 ppm of Examples 1 and 3. In this example, 80% conversion was obtained in 188 seconds. This value was obtained using a hydrogen consumption curve; the values shown in Table 1 allowed several points to be traced.
- Example 1 The procedure of Example 1 was repeated, replacing the ligand [2,3-bis(2,6-dimethylphenylimino)butane] with [2,3-bis(2,6-diisopropylphenylimino)butane] (see developed formula n o 4).
- the reaction time to achieve 80% 1,3-butadiene conversion was 22 seconds.
- the catalyst which was conventionally used in heterogeneous catalyst, could not directly produce cis 2-butene, but mainly 1-butene.
- the compared activity expressed in moles of converted 1,3-butadiene per minute and per gram of metal, was up to 2.4 times higher with the homogeneous iron-based catalyst. Further, the cis 2-butene selectivity was very high: close to 99%.
- the particular feature of the catalytic system was simply the very small quantity of 1-butene produced, for example for example 3 the very small quantity of n-butane formed with a remaining quantity of 1,3-butadiene of the order of 0.5%.
- Example 1 The operating procedure of Example 1 was used, but the composition of the substrate to be hydrogenated was different. It was a mixture composed of 50% of 1,3-butadiene and 50% of 1-butene.
- Example 1 The catalytic system used in Example 1 was used, but the nature of the feed to be hydrogenated was replaced with 2,4-hexadiene.
- the catalysis temperature was 22° C. and the hydrogen pressure was 1 MPa.
- the concentration of iron in the reaction medium was 200 ppm and the reaction time to reach 80% 1,3-butadiene conversion was 60 seconds.
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FR0208160A FR2841482B1 (fr) | 2002-06-28 | 2002-06-28 | Procede d'hydrogenation selective de composes polyinsatures en composes monoinsatures utilisant un catalyseur homogene |
FR02/08160 | 2002-06-28 | ||
PCT/FR2003/001811 WO2004002624A1 (fr) | 2002-06-28 | 2003-06-16 | Procede d'hydrogenation selective de composes polyinsatures en composes monoinsatures utilisant un catalyseur homogene |
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US20060129010A1 US20060129010A1 (en) | 2006-06-15 |
US7612245B2 true US7612245B2 (en) | 2009-11-03 |
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US10/519,355 Expired - Fee Related US7612245B2 (en) | 2002-06-28 | 2003-06-16 | Method for selective hydrogenation of polyunsaturated compounds into monounsaturated compounds using a homogeneous catalyst |
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US (1) | US7612245B2 (de) |
EP (1) | EP1519787B1 (de) |
JP (1) | JP4650805B2 (de) |
CN (1) | CN1665591B (de) |
DE (1) | DE60322060D1 (de) |
FR (1) | FR2841482B1 (de) |
WO (1) | WO2004002624A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US9422486B2 (en) | 2011-12-06 | 2016-08-23 | Petrochina Company Limited | Selective hydrogenation catalyst for unsaturated compound |
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WO2006007703A1 (en) * | 2004-07-16 | 2006-01-26 | Simon Fraser University | Phosphonium ionic liquids as recyclable solvents for solution phase chemistry |
CN100457268C (zh) * | 2006-09-08 | 2009-02-04 | 浙江大学 | 离子液体支载的乙酰丙酮金属的催化剂及制备方法 |
FR2915406B1 (fr) * | 2007-04-26 | 2010-03-12 | Inst Francais Du Petrole | Composition catalytique a base de nanoparticules contenant un ligand azote dans un liquide ionique, procede de preparation, procede d'hydrogenation d'une charge olefinique |
EP2140935A1 (de) * | 2008-07-04 | 2010-01-06 | Uop Llc | Selektives Hydrierungsverfahren mit einer geschichteten Katalysatorzusammensetzung und Herstellung des Katalysatoren |
CN103570489B (zh) * | 2013-11-05 | 2015-06-24 | 西北农林科技大学 | 一种铜催化的由炔烃制备顺式烯烃的方法 |
CN104629705B (zh) * | 2015-03-10 | 2017-06-13 | 中国地质大学(武汉) | 具供氢双配体结构稠油水热裂解催化降粘剂的制备方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3865893A (en) * | 1970-09-30 | 1975-02-11 | Judith G Thatcher | Conversion process utilizing homogeneous metal catalysts |
US3890400A (en) | 1972-02-24 | 1975-06-17 | Inst Francais Du Petrole | Process for selectively hydrogenating cyclic oligomers of butadiene |
US3917737A (en) * | 1970-07-09 | 1975-11-04 | Atlantic Richfield Co | Catalytic hydrogenation process |
US4357478A (en) | 1976-12-24 | 1982-11-02 | Institut Francais Du Petrole | Process for hydrogenating unsaturated compounds |
US6040263A (en) * | 1995-06-16 | 2000-03-21 | Institut Francais Du Petrole | Catalytic composition based on transition metal complexes, and a process for the hydrogenation of unsaturated compounds |
US20010005758A1 (en) | 1999-12-24 | 2001-06-28 | Ingrid Bach | Process for the codimerization of polyunsaturated fatty substances and olefins by iron complexes |
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JPS5181B2 (de) * | 1972-02-21 | 1976-01-05 | ||
FR2187730A1 (en) * | 1972-06-05 | 1974-01-18 | Inst Francais Du Petrole | Selective hydrogenation of hydrocarbons - using organonickel cpds with reducing agents as catalysts |
JPH0617326B2 (ja) * | 1985-01-29 | 1994-03-09 | 三菱化成株式会社 | 共役ジエン類の部分水素化方法 |
JPH072652B2 (ja) * | 1986-03-31 | 1995-01-18 | 日本ゼオン株式会社 | ジオレフインの選択的水素添加法 |
-
2002
- 2002-06-28 FR FR0208160A patent/FR2841482B1/fr not_active Expired - Fee Related
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2003
- 2003-06-16 JP JP2004516843A patent/JP4650805B2/ja not_active Expired - Fee Related
- 2003-06-16 EP EP03761619A patent/EP1519787B1/de not_active Expired - Lifetime
- 2003-06-16 WO PCT/FR2003/001811 patent/WO2004002624A1/fr active IP Right Grant
- 2003-06-16 DE DE60322060T patent/DE60322060D1/de not_active Expired - Lifetime
- 2003-06-16 US US10/519,355 patent/US7612245B2/en not_active Expired - Fee Related
- 2003-06-16 CN CN038152401A patent/CN1665591B/zh not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3917737A (en) * | 1970-07-09 | 1975-11-04 | Atlantic Richfield Co | Catalytic hydrogenation process |
US3865893A (en) * | 1970-09-30 | 1975-02-11 | Judith G Thatcher | Conversion process utilizing homogeneous metal catalysts |
US3890400A (en) | 1972-02-24 | 1975-06-17 | Inst Francais Du Petrole | Process for selectively hydrogenating cyclic oligomers of butadiene |
US4357478A (en) | 1976-12-24 | 1982-11-02 | Institut Francais Du Petrole | Process for hydrogenating unsaturated compounds |
US6040263A (en) * | 1995-06-16 | 2000-03-21 | Institut Francais Du Petrole | Catalytic composition based on transition metal complexes, and a process for the hydrogenation of unsaturated compounds |
US20010005758A1 (en) | 1999-12-24 | 2001-06-28 | Ingrid Bach | Process for the codimerization of polyunsaturated fatty substances and olefins by iron complexes |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9422486B2 (en) | 2011-12-06 | 2016-08-23 | Petrochina Company Limited | Selective hydrogenation catalyst for unsaturated compound |
US9611435B2 (en) | 2011-12-06 | 2017-04-04 | Petrochina Company Limited | Method for selective hydrogenation of unsaturated compound |
Also Published As
Publication number | Publication date |
---|---|
EP1519787B1 (de) | 2008-07-09 |
FR2841482B1 (fr) | 2006-12-29 |
CN1665591A (zh) | 2005-09-07 |
DE60322060D1 (de) | 2008-08-21 |
CN1665591B (zh) | 2011-05-25 |
FR2841482A1 (fr) | 2004-01-02 |
JP2005531625A (ja) | 2005-10-20 |
EP1519787A1 (de) | 2005-04-06 |
JP4650805B2 (ja) | 2011-03-16 |
WO2004002624A1 (fr) | 2004-01-08 |
US20060129010A1 (en) | 2006-06-15 |
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